Pyrithione biocides enhanced by zinc metal ions and organic amines

ABSTRACT

The present invention relates to a composition for prevention and treatment of dandruff characterized by comprising zinc pyrithione and zinc salt. The composition of the present invention has excellent effects in prevention and treatment of dandruff.

FIELD OF THE INVENTION AND THE RELATED ART

[0001] The present invention relates to a composition for prevention and treatment of dandruff. More particularly, it relates to a composition having excellent effects in prevention and treatment of dandruff through the improvement in an antibacterial activity against dandruff-causing bacteria by using zinc pyrithione and metal salt.

[0002] Component materials conventionally used in antidandruff agents have a limit of improvement in dandruff-preventing and dandruff-treating effects due to the dose limitation for the safety of human body. In addition, although the color of zinc pyrithione solution is milk-white, zinc pyrithione easily combines with ferrous ion contained in water or other components used for preparing the product to form ferrious pyrithione of dark blue, whereby the color of solution changes to dark blue, and, therefore, the appearance of the product is not good.

[0003] As part of a study to solve the problem, softening agents (i.e., chelating agents) were considered to be included in the zinc pyrithione solution. However, it is found that the agents capture zinc ions contained in zinc pyrithione, which deteriorates the bactericidal activity against dandruff-causing bacteria and the stability of the product.

TECHNICAL OBJECTS OF THE INVENTION

[0004] To solve the problems of the prior art, the present inventor has conducted a number of experiments and as a result, found that ferrious pyrithione is not formed if a zinc salt which has a high solubility in water is used, due to the common ion effect which makes it possible to maintain the color of product to be fine, and the bactericidal activity against dandruff-causing bacteria can be remarkably improved by controlling the ratio of the zinc sat to zinc pyrithione. The present invention is based on this finding.

CONSTITUTIONS AND EFFECTS OF THE INVENTION

[0005] The present invention relates to a dandruff-preventing and dandruff-treating composition characterized by comprising zinc pyrithione and zinc salt.

[0006] According to the present invention, there is provided a hair cosmetic composition having excellent effects in prevention and treatment of dandruff, where the effect of zinc pyrithione [trade name: Zinc Omadine (Oline)], i.e., the bactericidal activity against dandruff-causing bacteria, is enhanced by using zinc salt as a metal salt together with zinc pyrithione.

[0007] The zinc salt used in the dandruff-preventing and dandruff-treating composition of the present invention includes zinc chloride, zinc bromide, zinc iodide, zinc acetate and mixtures thereof. The ratio of zinc pyrithione/zinc salt is from 50/1 to 1/6, preferably from 10/1 to 1/4. If the ratio of zinc pyrithione/zinc salt is less than 50/1, the dandruff-preventing effect is poor, and if the ratio is more than 1/6, a further increase of the effect in proportion to the content is not observed, and, therefore, it is not economical.

[0008] The dandruff-preventing and dandruff-treating composition of the present invention can be useful for the hair cosmetic formulations such as hair shampoo, hair conditioner, etc.

[0009] The present invention is now further illustrated by, but is by no means limited to, the following Examples.

EXAMPLES 1-7 AND COMPARATIVE EXAMPLE 1

[0010] As shown in Table 1, 30% sodium lauryl sulfate, 30% polyoxyethylene sodium lauryl sulfate, palm oil fatty acid diethanolamide, propylene glycol, zinc pyrithione and a zinc salt selected from zinc chloride, zinc bromide, zinc iodide and zinc acetate, were added to and mixed with water. The mixture was heated to 60° C. to form a solution and then cooled to 40° C. After cooling, an appropriate amount of pigment (Blue 1), paroxybenzoate ester, perfume and citric acid were added to the mixture and mixed together. The mixture was then cooled to the room temperature to form a shampoo type formulation. TABLE 1 (% by weight) Com. Material Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 1 Sodium lauryl 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 sulfate (30%) Polyoxy- 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 ethylene Sodium lauryl sulfate (30%) Palm oil fatty 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 acid diethanol amide Propylene 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 glycol Zinc pyrithione 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Zinc chloride 0.1 0.5 1.5 — — — — — Zinc iodide — — — 0.1 0.5 — — — Zinc acetate — — — — — 0.1 0.5 — Pigment PQ PQ PQ PQ PQ PQ PQ PQ (Blue 1) Paraoxy- 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 benzoate ester Perfume PQ PQ PQ PQ PQ PQ PQ PQ (synthetic perfume SKP- 3473)* Citric acid PQ PQ PQ PQ PQ PQ PQ PQ Water Balance of 100% by weight

[0011] The effects of the shampoo products prepared in Examples 1-7 and Comparative Example 1, on the prevention and treatment of dandruff were evaluated according to the following test

[0012] Test on the Dandruff-Prevention Effects (1)

[0013] For 40 people of both sexes having a scalp condition wherein a relatively large amount of dandruff is found, a sample of each of the hair shampoo product of Table 1 was applied for 1 month. The hair was washed with a conventional shampoo before the start of the test, and the dandruff accumulated for three days after shampooing was collected and weighed. The hair was then washed with the shampoo composition of Table 1 once every two days for one month and, thereafter, the dandruff accumulated for three days after the final shampooing during the test period was weighed.

[0014] The collection of the accumulated dandruff was carried out by cleaning the head portion with vacuum suction device, and the dandruff reduction percentage was calculated as follows: $\quad {{{Dandruff}\quad {Reduction}\quad (\%)} = {\frac{{{Amount}\quad {of}\quad {dandruff}\quad {before}\quad {test}\quad ({mg})} - {{Amount}\quad {of}\quad {dandruff}\quad 1\quad {month}\quad {after}\quad {test}\quad ({mg})}}{{Amount}\quad {of}\quad {dandruff}\quad {before}\quad {test}\quad ({mg})} \times 100}}$

[0015] The test result is shown in Table 2. TABLE 2 Effect on prevention of dandruff Average Effective Ineffective Not certain Reduction (No. of (No. of (No. of Sample (%) people) people) people) Example 1 50.2 4 1 — Example 2 56.8 4 — 1 Example 3 52.2 5 — — Example 4 41.8 4 1 — Example 5 50.3 4 — 1 Example 6 38.0 5 — — Example 7 52.8 4 — 1 Comparative 30.4 2 2 1 Example 1

[0016] Test on the Dandruff-Preventing Effects (2)

[0017] 5, 1, 0.5, 0.1, 0.05 and 0.01% by weight of each of the shampoo compositions of Table 1 were added YM broth containing corn oil and Pityosporum orbiculare was then inoculated in the amount of 10⁵-10⁶ CFU (Colony Forming Unit)/ml. After incubating for 2 days, Minimal Inhibitory Concentration (MIC) and Minimal Bactericidal Concentration (MBC) were determined. The result is shown in Table 3. TABLE 3 Sample MIC (%) MBC (%) Example 1 0.01-0.05 0.05-0.1  Example 2 ≦0.01 0.01-0.05 Example 3 ≦0.01 0.01-0.05 Example 4 0.01-0.05 0.05-0.1  Example 5 ≦0.01 0.01-0.05 Example 6 0.01-0.05 0.05-0.1  Example 7 ≦0.01 0.01-0.05 Comparative 0.05-0.1  0.1-0.5 Example 1

[0018] As shown in Tables 2 and 3, the shampoo compositions of Examples 1-7 containing a zinc salt according to the present invention, are superior to the shampoo composition of Comparative Example 1 in the dandruff preventing and reducing effects, and the effect on preventing and reducing dandruff increase in proportion to the content of zinc salt.

EXAMPLES 8-14AND COMPARATIVE EXAMPLE 2

[0019] As shown in Table 4, cetyle alcohol, self-emulsifiable glycerol monostearate, paraoxybenzoate ester, 25% stearyldimethylbenzyl ammonium chloride, propylene glycol, zinc pyrithione and a zinc salt selected from zinc chloride, zinc bromide, zinc iodide and zinc acetate, were mixed and heated to 75° C. The mixture was then added into purified water of 75° C. and emulsified. The resultant was cooled to 40° C. After cooling, an appropriate amount of pigment, perfume and citric acid were added to the mixture and mixed together. The mixture was then cooled to the room temperature, and a hair conditioner composition was obtained. TABLE 4 (% by weight) Ex. Ex. Ex. Ex. Ex. Com. Material Ex. 8 Ex. 9 10 11 12 13 14 Ex. 2 Cetyle alcohol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Self-emulsifiable 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glycerol monostearate Paraoxybenzoate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 ester Stearyldimethyl 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 benzyl ammonium chloride (25%) Propylene glycol 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Zinc pyrithione 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Zinc chloride 0.1 0.5 1.5 — — — — — Zinc iodide — — — 0.1 0.5 — — — Zinc acetate — — — — — 0.1 0.5 — Pigment (Red 40) PQ PQ PQ PQ PQ PQ PQ PQ Perfume PQ PQ PQ PQ PQ PQ PQ PQ (synthetic perfume SKP- 3473)* Citric acid PQ PQ PQ PQ PQ PQ PQ PQ Water Balance of 100% by weight

[0020] The effects of the conditioner type products prepared in Examples 8-14 and Comparative Example 2, on dandruff and itchiness were evaluated according to the following test.

[0021] Test on the Dandruff-Preventing Effects (3)

[0022] For 40 people of both sexes having a scalp condition wherein a relatively large amount of dandruff is found, a sample of each of the hair conditioner products of Table 4 was applied for 1 month. The hair was washed with a conventional shampoo and rinsed with a conventional hair conditioner before the start of the test, and the dandruff accumulated for three days after shampooing was collected and weighed. The hair was then washed with the same conventional shampoo and rinsed with the hair conditioner composition of Table 4 once every two days for one month and, thereafter, the dandruff accumulated for three days after the final rinsing during the test period was weighed.

[0023] The collection of the accumulated dandruff was carried out in the same manner as in Example 1, and the results were evaluated as effective where the reduction percentage was 25% or greater. TABLE 5 Effect on prevention of dandruff Average Effective Ineffective Not certain Reduction (No. of (No. of (No. of Sample (%) people) people) people) Example 8 48.5 4 — 1 Example 9 55.4 5 — — Example 10 58.4 5 — — Example 11 37.6 4 — 1 Example 12 55.7 5 — — Example 13 40.9 4 — 1 Example 14 52.4 5 — — Comparative 30.3 2 1 2 Example 2

[0024] Test on the Dandruff-Preventing Effects (4)

[0025] 5, 1, 0.1, 0.05 and 0.01% by weight of each of the hair conditioner compositions of Table 4 were added YM broth containing corn oil and Pityrosporum orbiculare was then inoculated in the amount of 10⁵-10⁸ CFU (Colony Forming Unit)/ml. After incubating for 2 days, Minimal Inhibitory Concentration (MIC) and Minimal Bactercidal Concentration (MBC) were determined. The result is shown in Table 6. TABLE 6 Sample MIC (%) MBC (%) Example 8 0.01-0.05 0.05-0.1  Example 9 ≦0.01 0.01-0.05 Example 10 ≦0.01 0.01-0.05 Example 11 0.01-0.05 0.05-0.1  Example 12 ≦0.01 0.01-0.05 Example 13 0.01-0.05 0.05-0.1  Example 14 ≦0.01 0.01-0.05 Comparative 0.05-0.1  0.1-0.5 Example 2

[0026] As shown in Tables 5 and 6, the hair conditioner compositions of Examples 8-14 containing a zinc salt according to the present invention, are superior to the hair conditioner composition of Comparative Example 2 in the dandruff preventing and reducing effects, and the effect on preventing and reducing dandruff increase in proportion to the content of zinc salt 

1. An antimicrobial composition concentrate comprising pyrithione or a pyrithione complex in an amount of from about 0.05% to about 20 weight percent, a zinc source in an amount of from about 0.01% to about 5%, and an organic amine component in an amount of from about 30% to about 80%, said percents being based upon the total weight of the composition concentrate, said organic amine component comprising a first organic amine selected from the group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof, in combination with second organic amine selected from the group consisting of monomeric and polymeric forms of 1,2-alkyldiamines, monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine is present in said antimicrobial composition concentrate in an amount sufficient to insure that said amine component is soluble in said antimicrobial composition concentrate.
 2. The antimicrobial composition of claim 1, wherein said pyrithione complex is selected from the group consisting of pyrithione salts and adducts of pyrithione.
 3. The antimicrobial composition of claim 2, wherein said pyrithione salt is selected from the group consisting of sodium pyrithione, bismuth pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, zinc pyrithione, copper pyrithione, calcium pyrithione, magnesium pyrithione, strontium pyrithione, silver pyrithione, gold pyrithione, manganese pyrithione, an organic amine pyrithione, and combinations thereof.
 4. Canceled
 5. The antimicrobial composition of claim 1, wherein said zinc salt is selected from the group consisting of zinc acetate, zinc borate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, and combinations thereof.
 6. The antimicrobial composition concentrate of claim 1, wherein said first organic amine comprises a compound of the formula: R¹NH—(CHR²)_(n)—CHR³—OH   (Formula 1) wherein n=1 or 2 and R¹, R², and R³ are hydrogens or lower alkyl groups having a total number of carbons less than or equal to
 4. 7. The antimicrobial composition concentrate of claim 6, wherein said first organic amine is at least one compound selected from the group consisting of: ethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-(methylamino)ethanol, 2-(n-propylamino)ethanol, 2-(ethylamino)ethanol, 2-(isopropylamino)ethanol, and combinations thereof.
 8. The antimicrobial composition concentrate of claim 1, wherein said second organic amine comprises a compound of the formula: NR¹R²R³   (Formula 2) wherein R¹ is H, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, CH₃CH₂CH₂CH₂—, HO—CH₂—, and HO—CH(CH₃)—CH₂—, R² is H, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, CH₃CH₂CH₂CH₂—, HO—CH₂—CH₂—, HO—CH₂—CH₂—CH₂—, HO—CH(CH₃)—CH₂—, and HO—CH₂—C(CH₃)₂—, and R³ is HO—CH₂—CH₂—, HO—CH₂—CH₂—CH₂—, HO—CH(CH₃)—CH₂—, HO—CH₂—C(CH₃)₂—, (HOCH₂)₂C(CH₂CH₃), and HO—CH₂—CH₂—O—CH₂—CH₂—
 9. The antimicrobial composition concentrate of claim 8 wherein said second organic amine is selected from the group consisting of: diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, mixed isopropanolamines, 2-amino-2-methyl-1-propanol (also called AMP), 2-amino-2-ethyl-1,3-propanediol (also called AEPD), 2-(2-aminoethoxy)ethanol (also called diglycol amine),n-methyldiethanolamine, n,n-dimethylethanolamine, n,n-diethylethanolamine, n,n-dibutylaminoethanol, n,n-dimethylamino-2-propanol, and combinations thereof.
 10. Canceled
 11. Canceled
 12. The antimicrobial composition concentrate of claim 1, wherein said pyrithione, pyrithione salt or pyrithione complex comprises from about 5 to about 20 wt % of said antimicrobial composition, based on the total weight of said antimicrobial composition concentrate.
 13. The antimicrobial composition concentrate of claim 1, wherein said zinc source comprises from about 0.5 to about 5 wt % of said antimicrobial composition, based on the total weight of said antimicrobial composition concentrate.
 14. The antimicrobial composition concentrate of claim 1, wherein said organic amine and combinations of organic amines comprises from about 40 to about 70 wt % of said antimicrobial composition, based on the total weight of said antimicrobial composition concentrate.
 15. The antimicrobial composition concentrate of claim 1, further comprising a water or a water-miscible organic solvent.
 16. An antimicrobial composition concentrate, comprising pyrithione or a pyrithione complex in an amount of from about 0.05% to about 20 weight percent, a zinc source in an amount of from about 0.01% to about 5%, and an organic amine component in an amount of from about 30% to about 80%, said percents being based upon the total weight of the composition concentrate, said organic amine component comprising a first organic amine selected from an essential group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof, alone or in combination with second organic amine selected from the an additional group consisting, of 1,2-alkanolamines, 1,3-alkanolamines, monomeric and polymeric forms of 1,2-alkyldiamines, monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine is present in said antimicrobial composition concentrate in an amount sufficient to insure that said amine component is soluble in said antimicrobial composition concentrate, and further comprising a formaldehyde source in order to provide available formaldehyde in the antimicrobial composition concentrate.
 17. The composition concentrate of claim 16 wherein the formaldehyde source is selected from the group consisting of formaldehyde, cis 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, hexahydro-1,3,5-tris (2-hydroxyethyl)-s-triazine, 4,4-dimethyloxazolidine, 5-hydroxymethoxymethyl-1-1 aza-3,7-dioxabicyclo-octane, dimethyloldimethyldantoin, N,N″-methylene bis [N′-[hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea], N-(hydroxymethyl)-N-(1,3-dihydroxymethyl-2,5-dioxo-4-imidazolidinyl)-N′-(hydroxymethyl)urea, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, and combinations thereof.
 18. The antimicrobial composition concentrate of claim 16, wherein said formaldehyde source comprises from about 0.5 to about 30 wt % of said antimicrobial composition, based on the total weight of said antimicrobial composition concentrate. 19.-30. Canceled
 31. A method for providing a stable, soluble antimicrobial concentrate comprising from about 0.5% to about 20% of pyrithione, and a zinc source in an amount for from about 0.1% to about 10%, said method comprising incorporating into said concentrate a stabilizing effective amount of at least one organic amine component comprising a first organic amine selected from the group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof, in combination with a second organic amine selected from the group consisting of monomeric and polymeric forms of 1,2-alkyldiamines, monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine is present in said antimicrobial composition in an amount sufficient to insure that said amine component is soluble in said antimicrobial composition.
 32. The method of claim 33 wherein said stabilizing effective amount of said organic amine is from 30% to about 80% based upon the total weight of said organic amine plus said zinc source plus said pyrithione.
 33. A method for providing a stable, soluble antimicrobial concentrate comprising from about 0.5% to about 20% of pyrithione and a zinc source in an amount for from about 0.1% to about 10%, said method comprising incorporating into said concentrate a stabilizing effective amount of at least one organic amine component selected from the group consisting of comprising a first organic amine selected from the group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof alone or in combination with a second organic amine selected from the groups consisting of 1,2-alkanolamines, 1,3-alkanolamines, monomeric and polymeric forms of 1,2-alkyldiamines, monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine is present in said antimicrobial composition in an amount sufficient to insure that said amine component is soluble in said antimicrobial composition, said stable, soluble antimicrobial concentrate, further comprises from about 0.5% to 30% of formaldehyde or a formaldehyde source. 34.-38. Canceled 